EP0766708A2 - Organomineralisches silikat, copolymerer gerüststoff für waschmittel und waschmittelzusammensetzungen die diesen gerüststoff enthalten - Google Patents

Organomineralisches silikat, copolymerer gerüststoff für waschmittel und waschmittelzusammensetzungen die diesen gerüststoff enthalten

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Publication number
EP0766708A2
EP0766708A2 EP95923395A EP95923395A EP0766708A2 EP 0766708 A2 EP0766708 A2 EP 0766708A2 EP 95923395 A EP95923395 A EP 95923395A EP 95923395 A EP95923395 A EP 95923395A EP 0766708 A2 EP0766708 A2 EP 0766708A2
Authority
EP
European Patent Office
Prior art keywords
formula
sodium
potassium
order
ona
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP95923395A
Other languages
English (en)
French (fr)
Inventor
Eric Aubay
Jean-Pierre Cuif
Daniel Joubert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Chimie SAS
Original Assignee
Rhone Poulenc Chimie SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from FR9407529A external-priority patent/FR2721317B1/fr
Application filed by Rhone Poulenc Chimie SA filed Critical Rhone Poulenc Chimie SA
Publication of EP0766708A2 publication Critical patent/EP0766708A2/de
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/373—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen

Definitions

  • the present invention relates to a detergency builder ("builder”) silicon polymer based on an organomineral silicate copolymer having in particular good properties of primary and secondary detergency, as well as detergent compositions (household or industrial) containing said adjuvant. It also relates, as a new industrial product, to a silicon polymer based on an organomineral silicate copolymer having moreover surface-active properties.
  • builder silicon polymer based on an organomineral silicate copolymer having in particular good properties of primary and secondary detergency, as well as detergent compositions (household or industrial) containing said adjuvant. It also relates, as a new industrial product, to a silicon polymer based on an organomineral silicate copolymer having moreover surface-active properties.
  • detergent builder is understood to mean any constituent which improves the performance of the surfactants of a detergent composition.
  • a "builder” can act in multiple ways in a laundry environment. He can :
  • Silicates are conventionally known to be alkaline agents, to be corrosion inhibitors, to capture in complex form the ionic magnesium provided by calcareous waters. They are also used for a certain dispersing power, but they are only additions to complex adjuvant systems ("builders") which conventionally include mineral or organic sequestrants, alkaline precipitants such as sodium carbonate etc ... In their traditional form, therefore, play only a minor role as a detergency builder. They are also recognized as agglomeration and structural agents; they play this role in particular when they are present in suspensions or slurries before atomization, or when they are used as binding agents in the granulation processes of the compositions.
  • builders complex adjuvant systems
  • silicates are increasingly used in the form of solid products introduced into detergent powder compositions, in post-addition after the atomization tower. These products, of practical use for the preparation of final mixtures, are especially recommended in the case of formulas based on zeolites to avoid the problems of incompatibility between zeolite and silicate during the drying of a suspension containing these compounds. These solid products are obtained by separate atomization of the silicate solution, then optionally are then modified by granulation or compaction, so as to increase their average diameter, possibly their density and to decrease their tendency to dusting and caking in a humid atmosphere. This type of product is always conventionally used in low doses and simply as a complement to conventional adjuvant systems ("builders"), generally based on zeolite as the main adjuvant. They do not have any particular properties distinguishing them from traditional silicates.
  • builders generally based on zeolite as the main adjuvant. They do not have any particular properties distinguishing them from traditional silicates.
  • alkali silicate More recently, a different form of alkali silicate has been proposed as a detergency builder, with improved exchange properties with respect to calcium and magnesium in hard water and having a higher dispersing power.
  • This product is a hydrated silicate; more particularly this silicate can be supported by sodium carbonate and thus be in the form of cogranules.
  • Such products are described in particular in applications EP-A-0 488 868 and EP-A-0561 656. It has been proposed to use aqueous solutions of mixtures of alkali metal silicates and alkali metal alkylsiliconates for waterproofing masonry (US-A-2,905,562).
  • Document SU-A-971 865 discloses the use as a defoamer for drilling muds, of a composition obtained by mixing an alkali metal silicate, a potassium siliconate, a water-soluble metal salt multipurpose and water, filtration and drying.
  • the anionic siiiconates of formula above have also been described as agents for stabilizing alkali metal silicates by forming copolymers and for dissolving said silicates in aqueous alcoholic antifreeze formulations (US-A-4352742, 4354002, 4362 644, 4370 255, 4333 843, 4344860, 4503242).
  • the subject of the invention is a silicone polymer detergency builder based on an organomineral silicate copolymer, a silicon polymer capable of being obtained by condensation polymerization.
  • (a + __) can range from 1 to 3, with a equal to or greater than 1 and h equal to 0 or 1,.
  • R represents a similar or different hydrocarbon group containing from 1 to 20 carbon atoms, preferably from 1 to 18 carbon atoms, optionally halogenated and optionally containing one or more nitrogen or oxygen heteroatoms.
  • Y is a hydroxyl group,
  • n + ⁇ is less than or equal to 4, with n possibly ranging from 1 to 3 and ⁇ greater than or equal to 1,
  • M represents an ammonium cation or preferably an alkali metal
  • R and n have the definition given above,
  • X represents an alkoxyl group containing from 1 to 20 carbon atoms, a hydroxyl group or a halogen atom.
  • alkali metal silicates which can be used for the preparation of the silicone polymeric adjuvant based on organomineral silicate copolymer, mention may be made of those of ammonium, sodium, potassium, lithium, and very particularly those of sodium or potassium.
  • alkyl radicals such as methyl, ethyl, propyl, butyl, hexyl, octyl, dodecyl, octadecyl, etc .
  • cycloalkyl radicals such as cyclopentyl, cyclohexyl, cycloheptyl ...
  • aryl radicals such as phenyl, naphthyl ...
  • arylalkyl or alkylaryl radicals such as tolyl, xylyl ...
  • alkenyl radicals such as vinyl, allyl ...
  • organic silicon compounds (B) which can be used for the preparation of the silicon polymeric adjuvant, mention may be made very particularly of: sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OK) 3, sodium or potassium propylsiliconates of formula C3H7 Si (ONa) 3 or C3H7 Si (OK) 3, sodium butylsiliconates or potassium of formula C4H9 Si (ONa) 3 or C4H9 Si (OK.3, sodium or potassium hexylsiliconates of formula C ⁇ H-
  • Cyclooctamethylt etrasiloxane D4 ⁇ , ⁇ bis (hydroxy) polydimethylsiloxanes, ⁇ , ⁇ bis (hydroxy) polymethyloctylsiloxanes, polydimethylsiloxanes, polymethyloctylsiloxanes, or other silicone oils or resins comprising methylsiloxane or dimethylsiloxane units.
  • the reaction leading to the silicone polymeric adjuvant of the invention can be carried out by bringing together the compounds (A) and (B).
  • the silicate (A) can be in the form of an aqueous solution advantageously containing on the order of 5 to 55% by weight of dry matter, preferably on the order of 35 to 55%, or in the form of a solid. pulverulent or granular, amorphous or crystalline, which may contain from 0 to 50% water approximately.
  • the compound (B) is preferably used, depending on its solubility in water, in the form of an aqueous solution, an emulsion or an aqueous microemulsion.
  • potassium methylsiliconate has the property of being soluble in water in significant proportions, about 50% by weight.
  • other compounds comprising fewer Si-OH or Si-OM bonds such as those of the high molecular weight polyorganosiloxane type, may be used as an emulsion or microemulsion in water.
  • Another possibility for the compound (B) to be in a sufficiently reactive form consists in carrying out a hydrolysis of the compound (B) with the alkaline silicate (A), preferably at more than 50 ° C .; hydrolysis leads to smaller molecules which can react with the silicate via newly formed terminal SiO units.
  • the reaction mixture can therefore be a liquid (A) / liquid (B) mixture or a powder (A) / liquid (B) mixture.
  • Compounds (A) and (B) can be mixed in very large proportions.
  • about 10 to 99.9 parts of (A) are used for 90 to 0.1 parts of (B), expressed in dry weight.
  • the reaction mixture comprises at least 40% of compound (A) relative to the dry weight of mixture (A) + (B).
  • the mixture obtained can be analyzed by RN of silicon 29.
  • This analysis method makes it possible to measure the number of Si atoms close to the Si atoms coming from the compound (A) and the Si atoms coming from the compound (B), and makes it possible to specify the environment of the Si-R sites of the compound (B).
  • the copolymerization may or may not take place spontaneously, but to a limited extent, depending on the physico-chemical conditions of implementation.
  • the copolymerization can be initiated or increased, in particular:
  • the copolymerization can take place spontaneously.
  • a sodium silicate with a Si ⁇ 2 / a2 ⁇ molar ratio of 3.5 having a pH of about 11.5
  • potassium methylsiliconate whose pH is 13.5
  • an intermediate product of copolymerization will be obtained resulting from the drop in pH of potassium methylsiliconate and the rise in pH of sodium silicate.
  • the reaction product can then be in liquid or solid form, depending on the technique used to complete the copolymerization.
  • the product can be used in both forms.
  • the product obtained is a powder; in the case of static drying, a solid mass is obtained which can be ground into a powder; when the copolymerization is obtained by evaporation of water from the reaction mixture, the two stages of copolymerization and solid shaping can be carried out simultaneously in the same drying device.
  • the mineral support can be chosen in particular from sodium carbonate, sodium sulfate, sodium metasilicate, sodium borate, sodium perborate, phosphates or polyphosphates such as trisodium phosphate, sodium tripolyphosphate ... , these products being alone or mixed with each other; preferably using products with detergency activity and more particularly sodium carbonate, drying can be more moderate than in the previous case, given the ability of the support to retain part of the water initially present in the solution.
  • a subject of the invention is also the adjuvants comprising the copolymerization product of (A) and (B) in an absorbed and / or adsorbed form on an inorganic support.
  • the degree of dryness of the adjuvant of the invention, supported or not, is controlled and that the water content in the final product remains in the range from 1 to 40 % of water compared to the dry product, preferably from 5 to 30%.
  • the adjuvants of the invention have good primary and secondary detergency properties, in particular anti-redeposition.
  • the present invention therefore also relates to the use of silicon polymers based on the above organomineral silicate copolymer, supported or not, as adjuvants in detergent compositions.
  • the subject of the present invention is also, as a new industrial product, a silicon polymer based on an organomineral silicate copolymer, a polymer characterized in that it is capable of being obtained by copolymerization by condensation,
  • R m Si (OM) 4_ m (1) formula in which,. m can range from 1 to 3, and preferably is equal to 1 or 2, .
  • R represents a similar or different linear or branched alkyl group containing
  • M represents a proton, an ammonium cation or preferably an alkali metal
  • average degree of connectivity des n of the silicon atoms derived from the organic silicon compound (B1) means the average number of vicinal silicon atoms linked, via an oxygen bridge -O-, to each silicon atom derived from said organic silicon compound (B1), regardless of the origin of said vicinal silicon atoms, whether the latter come from alkali metal silicate (A) or from the organic silicon compound (B1).
  • ⁇ n ⁇ i ⁇ j where i varies between 0 and 3 and ⁇ j represents the proportion of silicon atoms, expressed as a decimal fraction between 0 and 1, coming from the organic silicon compound linked to i vicinal silicon atoms via of an oxygen bridge -O-.
  • the distribution of the connectivity degrees ⁇ j is measured by NMR of silicon 29 on said silicon polymer in the form of a solid product.
  • the NMR spectra of silicon 29 are recorded on a BRUKER spectrometer of model MSL 300, equipped with a MAS 7mm BRUKER probe of the HP WB 73A series of type MAS 7.DB.CP.BB.VTN.
  • the spectra are acquired under cross polarization, high power decoupling and rotation at the magic angle with the following parameters:
  • the average degree of connectivity Q n of the silicon atoms derived from the alkali metal silicate (A), which can be established in a manner analogous to that concerning ⁇ n , is not a critical element of the present invention.
  • This average degree of connectivity Q n is different from zero and less than 4. It has been found that this is generally less than 3, for example of the order of 2 to 2.7.
  • Said silicon polymer has a water content of the order of 5 to 30%, preferably of the order of 15 to 30% of its weight. This water content can be evaluated by measuring the loss on ignition of said silicon polymer at 700 ° C.
  • alkali metal silicates which can be used for the preparation of said silicon polymer based on organomineral silicate copolymer, mention may be made of those of ammonium, sodium, potassium, lithium, and very particularly those of sodium or potassium.
  • siiiconates of formula (1) there may be mentioned in particular those of sodium or potassium, and very particularly the sodium or potassium methylsiliconates of formula CH3 Si (ONa) 3 or CH3 Si (OK) 3, sodium propylsiliconates or potassium of formula C3H7 Si (ONa) 3 or C3H7 Si (OK) 3, sodium or potassium butylsiliconates of formula C4Hg Si (O a) 3 or C4H9 Si (OK) 3, sodium or potassium hexylsiliconates of formula C ⁇ Hi3 Si (ONa) 3 or C ⁇ H-13 Si (OK) 3, sodium or potassium octylsiliconates of formula CsH- ( 7 Si (O a) 3 or CsH-
  • the condensates of the siiiconates of formula (1) are considered to be soluble in said alkali metal silicate (A) in aqueous solution, when their solubility is at least 50% by weight in an aqueous alkali metal silicate solution (A) containing from 35 to 55% by weight of active material.
  • condensates of the siiiconates of formula (1) mention may be made particularly of commercial solutions of potassium methylsiliconate containing in the order of 40 to 50% by weight of active material.
  • Said silicon polymer based on organomineral silicate copolymer can be obtained by precopolymerization of at least one alkali metal silicate (A) and at least one organic silicon compound (B1) by mixing the two reactants (A) and ( B1), followed by a drying operation to continue the copolymerization to the desired reduced degree of average connectivity ⁇ n / m.
  • the precopolymerization operation can be carried out by contacting an aqueous solution of at least one alkali metal silicate (A) containing from 35 to 55%, preferably from 35 to 50% by weight of active material, with at least one siliconate of formula (1), preferably in aqueous solution containing about 40 to 50% of its weight of active material, at a temperature of about 20 to 100 ° C.
  • This precopolymerization operation has rapid kinetics; it generally lasts from 1 to 10 minutes.
  • the aqueous solution obtained is then dried at a temperature of the order of 40 to 250 ° C., for a period such that the silicon polymer obtained has a copolymerization rate corresponding to the reduced average degree of connectivity ⁇ n / m of the silicon atoms derived from the organic silicon compound (B1) of the order of 0.5 to less than 1, preferably of the order of 0.65 to 0.99.
  • This drying operation can be carried out by any means, for example in a rotary oven, by atomization, in an oven, in a rapid mixer, in a "flash" dryer, in a fluidized bed ...
  • the solid obtained can then be ground according to known techniques, until a particle size powder suitable for the future use of said silicon polymer is obtained.
  • the average particle diameter can generally be of the order of 150 to 800 ⁇ m.
  • said silicon polymer based on organomineral silicate copolymer is in the adsorbed and / or adsorbed state on a water-soluble mineral support, preferably consisting of sodium carbonate; the amount of said support can be of the order of 30 to 75 parts, preferably of the order of 40 to 70 parts by weight per 100 parts of finished product (the finished product considered consists of said silicon polymer with its water content and of said support) .
  • a variant of the process for obtaining the silicon polymer consists in spraying the solution obtained by precopolymerization, onto a water-soluble mineral support, of preferably consisting of sodium carbonate, and drying successively or simultaneously with its spraying, said solution at a temperature of the order of 40 to 250 ° C., for a period such that the silicon polymer obtained has a rate of copolymerization corresponding to the degree of connectivity reduced means ⁇ n / m of the silicon atoms derived from the organic silicon compound (B) of the order of 0.5 to less than 1, preferably of the order of 0.65 to 0.99, and such that said supported silicon polymer contains an amount of water of the order of 5 to 30%, preferably of the order of 15 to 30% relative to said silicon polymer expressed as dry.
  • the amount of said support can be of the order of 30 to 75 parts, preferably of the order of 40 to 70 parts by weight per 100 parts of finished product (the finished product considered consists of said silicon polymer with its water content and of said support) .
  • the new silicon polymer derived from an alkali metal silicate (A) and from an organic silicon compound (B1), supported or not, as well as the silicon polymers derived from an alkali metal silicate ( A) and polyorganosiloxanes or organosilanes (B), supported or not are capable of reducing the surface tension of aqueous media.
  • This surface tension lowering measurement can be carried out using a LAUDA brand tensiometer by the ring method.
  • the present invention therefore also relates to a surfactant detergency builder based on said silicon polymers, supported or not, as well as the use of said surfactant adjuvants in detergent compositions.
  • Said detergency builders, optionally surfactants, which are the subject of the invention, are endowed in particular with water-repellent, dispersing and sequestering properties of calcium and magnesium ions, anti-redeposition of soiling, anti-corrosion of metals .
  • They can be used in particular as a sequestering agent for calcium ions, optionally as an anionic surfactant, in household or industrial detergency (household or industrial washing of textiles or dishes, treatment of industrial surfaces such as floors, walls, tiles, sanitary, etc.). .), for anticorrosion and water repellent treatment of metal surfaces, for cleaning dealing with car bodies, heavy vehicle chassis or construction equipment ...
  • detergent composition means any formulation which can be applied in the field of household cleaning (powder detergent formulations intended for use both in a machine, washing machine or dishwasher for example, as in the hand or in other means) or industrial (treatment of hard industrial surfaces such as floors, walls, tiles, sanitary ).
  • said detergent composition can contain from about 1 to 60%, preferably from about 5 to 50% of its weight, expressed as dry matter, of said optionally surfactant silicon polymeric adjuvant.
  • alkyl ester sulphonates of formula R-CH (S ⁇ 3M) -COOR ', where R represents an alkyl radical Cs-20> preferably C10-C16.
  • R ' an alkyl radical in C- -CQ, preferably in C1-C3 and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium .. .) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ).
  • Mention may very particularly be made of methyl ester sulfonates whose radicals R is C-
  • alkyl sulfates of formula ROSO3M where R represents a C10-C24 alkyl or hydroxyalkyl radical. preferably in C12-C20 and very particularly in C12-C18.
  • M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0, 5 to 3 OE and / or OP motifs; .
  • the alkylamide sulfates of formula RCONHROSO3M where R represents a C2-C22 alkyl radical. preferably in C6-C20.
  • R 'a C2-C3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having an average of 0, 5 to 60 OE and / or OP patterns;
  • the salts of C8-C24 preferably C14-C20 saturated or unsaturated fatty acids.
  • glycerolamides derived from N-alkylamines (US-A-5,223,179 and FR-A-1, 585.966)
  • polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
  • amine oxides such as alkyl oxides CI Q-C-
  • BUILDERS - ADJUVANT DETERGENCE AGENTS
  • polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates of alkali metals, ammonium or alkanolamines
  • alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates)
  • zeolites A, P, X ...; zeolite A with a particle size of the order of 0.1 -10 micrometers is preferred organic adjuvants
  • water-soluble polyphosphonates ethane 1-hydroxy-1, 1-diphosphonates, methylene salts diphosphonates .
  • polycarboxylate ethers oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts.
  • hydroxypolycarboxylate ethers oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts.
  • citric acid and its salts citric acid and its salts, mellitic acid, succinic acid and their salts.
  • polyacetic acid salts ethylenediaminetetraacetates, nitrilotriacetates,
  • polyacetal carboxylic esters polyaspartic acid, polyglutamic acid and their salts
  • BLEACHING AGENTS in amounts of about 0.1-20%, preferably about 1 -10% by weight, optionally combined with BLEACHING ACTIVATORS, in amounts of about 0.1-60%, preferably d '' about 0.5-40% by weight, agents and activators such as bleaches
  • perborates such as sodium perborate monohydrate or tetrahydrate.
  • peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably combined with a bleach activator generating in situ in the washing medium, a peroxyacid carboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, Toctaacetyl lactose ...
  • percarboxylic acids and their salts such as magnesium monoperoxyphthalate hexahydrate, metachloroperbenzoate magnesium, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, peroxysuccinic acid nonylamide, T decyldiperoxysuccinic acid.
  • These agents can be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.
  • Non-oxygenated bleaching agents acting by photoactivation in the presence of oxygen
  • agents such as sulphonated aluminum phthalocyanines and / or zinc.
  • ANTI-FOULING AGENTS in amounts of the order of 0.01-10% , preferably about 0.1-5%, and most particularly on the order of 0.2-3% by weight, agents such as.
  • cellulose derivatives such as cellulose hydroxyethers, methylcellulose, methylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose.
  • polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048).
  • polyvinyl alcohols such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048).
  • polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units with a molar ratio (number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10 / 1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230 , US-A-3 893929, US-A-4 116 896, US-A-4702857, US-A-4770 666); .
  • sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1, 2 propylene diol, having from 1 to 4 sulfonated groups (US-A-4968451)
  • polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated by ethyl or methyl units (US-A-4,711,730) or polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or groups anionic sulfopolyethoxy (US-A-4,721,580), sulfoaroyl (US-A-4877 896)
  • polyesters-polyurethanes obtained by reaction of a polyesters with a molecular mass of 300-4000 in number obtained from adipic acid and / or tereptalic acid and / or sulfoisophthalic acid and a diol of mass less than 300, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and a diisocyanate ((FR-A-2 334698) - ANTI-REDEPOSITION AGENTS, in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as
  • ethoxylated monoamines or polyamines polymers of ethoxylated amines (US-A-4,597,898, EP-A-11,984)
  • the sulfonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulfosuccinate and diethylene glycol (FR-A-2236926)
  • polyvinylpyrollidones - CHELATING AGENTS of iron and magnesium in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, agents such as
  • aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethyl ethylenediaminetriacetates, nitrilotriacetates
  • aminophosphonates such as nitrilotris (methylene phosphonates).
  • polyfunctional aromatic compounds such as dihydroxydisulfobenzenes
  • molecular weight polyethylene glycols of the order of 1000 to 50,000
  • agents such as
  • aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as paraffins, waxes.
  • N-alkylaminotriazines . monostearylphosphates, monostearyl alcohol phosphates
  • proteases amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
  • alcohols methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin
  • the test simulates a simplified machine wash, using a tergotometer. It consists in washing test pieces of soiled fabrics in a standard and uniform manner at 40 ° C, with only the adjuvant to be tested at a concentration of 1.75 g (active ingredient) / liter. The washing lasts 20 minutes and the detergency is evaluated by measuring, using a colorimeter, the whiteness of the pieces of fabric, before and after washing.
  • test pieces are manufactured by the CFT (Center For Test materials). They have the following characteristics:
  • the tergotometer is a device made up of 6 2-liter stainless steel pots on which stirrers are fitted that are set to 100 cycles per minute (100 round trips). The pots are placed in a water tank regulated at 40 ° C.
  • the 16 soiled test pieces and the 4 unsoiled test pieces are introduced one by one into the jar of the tergotometer.
  • the adjuvant is added, then cold water is introduced.
  • the fact of using cold water is characterized by a decrease in the temperature of the thermostatically controlled bath. However the temperature reaches 40 ° C in a time less than
  • the fabrics are rinsed three times with tap water, then wrung by hand and dried flat individually between two sheets of white absorbent paper.
  • the fabrics are again put between two sheets of clean absorbent paper, and ironed in the freezer at a temperature close to 110 ° C.
  • the measurements are carried out with the "LUC1 100" colorimeter before and after washing according to the "L", “a”, “b” system (scale from black to white, from green to red and from blue to yellow) to measure the power detergent for the adjuvants tested (increased whiteness of the pieces of soiled tissue).
  • the precopolymerized solution obtained is homogenized for 15 minutes.
  • the copolymerization is continued by drying the solution in an APV atomizer sold by APV (temperature of the inlet gases: 250 ° C; temperature of the outlet gases: 120 ° C; residence time of approximately 1 second).
  • the solid obtained is ground until particles of 800 ⁇ m on average are obtained and analyzed by NMR of silicon 29.
  • the surface tension of the solution at the water-air interface obtained is measured using a LAUDA brand tensiometer, using the ring method. This is 49.3. 10- 5 N / cm, against 70.6. 10- 5 N / cm for water alone.
  • EXAMPLE 2 The operation described in the preceding example is repeated, replacing the spray drying step, with a 5 mm thin layer drying operation in an oven at 105 ° C. for 48 hours.
  • the solid obtained is ground until particles of 800 ⁇ m on average are obtained and analyzed by NMR of silicon 29.
  • the NMR measurements carried out on the solid show that the product obtained has
  • the particles are then dissolved in water so as to obtain 2 g / l of dry matter.
  • the surface tension of the solution at the water-air interface obtained is measured using a LAUDA brand tensiometer, using the ring method.
  • the two solutions are left to react at ambient temperature for approximately 30 minutes.
  • the solution is then diluted with deionized water until a final concentration of 100 g / l expressed in silicon is obtained.
  • the proportions of the degrees of connectivity ⁇ j are obtained by integrating the ranges of the spectrum acquired by the INEPT sequence under the conditions given by P. Lux, F. Brunet, H. Desvaux and J. Virlet in "Magnetic Resonance in Chemistry Vol 31, 623 -631 (1993). These measurements show that the product obtained has
  • the surface tension of the solution at the water-air interface obtained is measured using a LAUDA brand tensiometer, using the ring method.
  • Example 1 The toperation described in Example 1 is repeated, replacing the spray drying step, with a drying operation in a thick layer of 2 cm in a drying oven.
  • the particles are then dissolved in water so as to obtain the dry matter concentration given in the table below.
  • the surface tension of the solution at the water - air interface obtained (measurement using a LAUDA brand tensiometer, by the ring method), as a function of the concentration of the solution, is shown in the next board.
  • Example 4 The toperation described in Example 4 is repeated, using 1 part of siliconate for 99 parts of silicate.
  • the solid obtained has a water content of 24.8% (evaluation by measurement of the loss on ignition at 700 ° C. of the product)
  • the precopolymerized solution obtained is homogenized for 30 minutes.
  • the copolymerization is continued by drying the solution in an oven at 105 ° C. in a thick layer of 4 cm for 7 days.
  • the solid is ground and then dissolved.
  • the characteristics of the product obtained are as follows
  • Example 24 The adjuvant from Example 18 is again ground in a mortar, then dried in a tetuvian in a thin layer of 5 mm, at 70 ° C. for 24 hours. Their characteristics are as follows
  • the cogranules formed are evacuated and left to remain in the air for 2 hours at room temperature.
  • the anti-redeposition properties of the adjuvants of the invention can be demonstrated by comparison of the detergency results on standard white fabrics cotton CN1 and polyester / cotton PCN1, obtained according to the test described above, with those obtained by replacing the adjuvant of the invention with the same amount (1.75 g / l) of atomized sodium silicate with a Si ⁇ 2 / Na2 ⁇ ratio of 2.
  • FIG. 1 shows the sequestration capacity of the adjuvants of examples 1, 18 and 16.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Silicon Polymers (AREA)
EP95923395A 1994-06-20 1995-06-16 Organomineralisches silikat, copolymerer gerüststoff für waschmittel und waschmittelzusammensetzungen die diesen gerüststoff enthalten Ceased EP0766708A2 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9407529 1994-06-20
FR9407529A FR2721317B1 (fr) 1994-06-20 1994-06-20 Produit dérivé de silicate possédant des propriétés builder et tensioactives.
FR9502029A FR2721318B1 (fr) 1994-06-20 1995-02-22 Polymère silicié organominéral, son utilisation comme agent tensio-actif dans les compositions détergentes et compositions détergentes contenant ledit polymère.
FR9502029 1995-02-22
PCT/FR1995/000794 WO1995035338A2 (fr) 1994-06-20 1995-06-16 Adjuvant de detergence a base d'un copolymere silicate organomineral et compositions detergentes le contenant

Publications (1)

Publication Number Publication Date
EP0766708A2 true EP0766708A2 (de) 1997-04-09

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EP95923395A Ceased EP0766708A2 (de) 1994-06-20 1995-06-16 Organomineralisches silikat, copolymerer gerüststoff für waschmittel und waschmittelzusammensetzungen die diesen gerüststoff enthalten

Country Status (6)

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EP (1) EP0766708A2 (de)
AU (1) AU2796595A (de)
FR (1) FR2721318B1 (de)
IL (1) IL114240A0 (de)
TW (1) TW306930B (de)
WO (1) WO1995035338A2 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2728583B1 (fr) * 1994-12-23 1997-01-31 Rhone Poulenc Chimie Compositions detergentes a base d'un copolymere silicate organomineral, utilisation dudit copolymere comme agent alcalin non corrosif et protecteur du verre et de la vaisselle
FR2741887A1 (fr) * 1995-12-01 1997-06-06 Rhone Poulenc Chimie Polymere silicie supporte et agent alcalin protecteur du verre et de la vaisselle a base dudit polymere silicie supporte
JP6786716B2 (ja) * 2017-04-04 2020-11-18 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ 反応性シロキサンおよびその製造方法

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
FR1324490A (fr) * 1961-04-26 1963-04-19 Union Carbide Corp Nouveaux copolymères d'organosiloxanes-silicates
IT1160682B (it) * 1977-10-14 1987-03-11 Po Corp. Composizioni detergenti con coadiuvante di silano-zeolite
US4157978A (en) * 1978-03-13 1979-06-12 The Procter & Gamble Company Modified silicates
JPS5571767A (en) * 1978-11-21 1980-05-30 Osaka Packing Seizosho:Kk Corrosionproof composition
US4244849A (en) * 1979-08-06 1981-01-13 Dow Corning Corporation Silicone emulsion which provides an elastomeric product and methods for preparation
US4549979A (en) * 1984-03-27 1985-10-29 Dow Corning Corporation Detergent composition with siliconate-silicate copolymer
JP3153586B2 (ja) * 1991-10-15 2001-04-09 鐘淵化学工業株式会社 ケイ素系ハイブリッド材料

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9535338A2 *

Also Published As

Publication number Publication date
TW306930B (de) 1997-06-01
AU2796595A (en) 1996-01-15
WO1995035338A3 (fr) 1996-02-01
FR2721318A1 (fr) 1995-12-22
FR2721318B1 (fr) 1996-12-06
WO1995035338A2 (fr) 1995-12-28
IL114240A0 (en) 1995-10-31

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